Pyrolysis reactor with optimized reaction sequencing

ABSTRACT

System and method for processing pyrolyzable materials in order to recover usable end products are disclosed. The pyrolysis process comprises a number of stages. First pre-treating is to reduce moisture content to approximately 15%. Second is to optimize the volatile organic under the heat and vacuum. This treatment stage is carried out at the temperature between 350 to 400° C. Next, the material is treated with heat and vacuum to produce hot gas and solid carbon residue. This stage is carried out at the temperature up to 800° C. The solid carbon residue can be separated from the hot gas, the volatile organic materials condensed to produce liquid hydrocarbon and gas products. Pyrolysis processes and system according to the present invention are able to thermally decompose carbon-containing materials, including, but not limited to, tires and other rubber-containing materials, hydrocarbon-containing products including pyrolysis oil, used oil and lubricants, organic wastes and alike, carbon containing minerals like brown and bituminous coal, oil shale and oil bearing schists. System and pyrolysis methods according to aspects of the present invention may be successful on a commercial scale.

BACKGROUND OF THE INVENTION

The invention relates to a device for subjecting carbon contained materials to pyrolysis, which device comprises: a reactor with a housing and a reactor space present therein; a first feed for contained materials material or other organic material connecting to the heated up to 400° C. upper zone of this reactor space; a second feed for heated space, connected to the upper side of this reactor space; a first discharge for pyrolysis gas connecting to the upper zone of this reactor space at a distance from the first feed; and a second discharge connecting to the middle zone of this reactor space; and discharge for solid material, for instance carbon material, connecting to the underside of this reactor space. Such a reactor is known in many embodiments from, among others, U.S. Pat. No. 1,777,449, U.S. Pat. No. 3,507,929 and U.S. Pat. No. 4,210,491.

In pyrolysis process wherein a hydrocarbon containing mixture is heated to decomposition or cracking temperature, a certain portion of the combined or organic carbon present in the hydrocarbon is converted to its elemental state. The undesirable phenomenon is that fine particles accumulate on solid surface of the reactor, and cause blockage thereof after a period of time. Problem of the carbon deposits formation during the pyrolysis process is less serious for the process temperature of 1000° C. and higher.

Pyrolysis processes of hydrocarbons and hydrocarbon-hydrogen mixtures at temperatures between 1450-2000° C. are described for example in U.S. Pat. No. 3,156,733 or U.S. Pat. No. 3,156,734. However, as the temperature level of operation during pyrolysis increases, the number of construction materials which can be used is drastically reduced.

At temperature level of 1400 to 1500° C., even the refractory oxides begin to suffer under attack by hydrogen, carbon or hydrocarbons during the pyrolysis process. In the range of 1500 to 2000° C. and higher, there are no readily available materials which can be economically used, have the good mechanical properties required, resist the attack of hydrogen, carbon and hydrocarbons, and also have oxidation resistance over long periods of operating time.

High temperature reactions and processes typically require more complex, costly, and specialized equipment to tolerate the intense heat and physical stress conditions, and leads to lowering the upper limits of temperature for many of the processes and facilities.

In addition to physical temperature limitations for reactor materials, many prior art reactor materials that are inert at lower temperatures may become susceptible to chemistry alterations at high temperature, leading to premature equipment degradation.

Further complicating the material stability and reliability issue has been exposure to large, cyclic temperature swings encountered during many pyrolysis processes. Changes in temperature and feedstock flow can impose severe physical strength and toughness demands upon the materials at high temperature. Material life expectancy at high temperature can be severely limited. Reactor component functions and shapes have been limited for high severity services.

Due to high temperatures involved in cyclic pyrolysis reactors, generally only ceramic components have the potential to meet the materials characteristics needed in such aggressive applications. Ceramics components generally can be categorized in three material categories: engineering grade, insulation grade, and refractory grade.

The term “engineering grade” has been applied to ceramic materials which typically have very low porosity, high density, relatively high thermal conductivity, and comprise a complete component or a lining. Examples include dense forms of aluminum oxide (Al₂O₃), silicon nitride (Si₃N₄), silicon carbide (SiC), silicon aluminum oxynitride (SIALON), zirconium oxide (ZrO₂), transformation-toughened zirconia (TTZ), transformation-toughened alumina (TTA), and aluminum nitride (AlN).

Insulation grade ceramics are typified by relatively high porosity. Many may have fibrous crystalline grain structures and are more porous than engineering grade ceramics, have lower density, and have lower thermal conductivity than engineering grade ceramics.

Many refractory grade ceramics typically have porosity, strength, and toughness properties intermediate to such properties in engineering grade and insulation grade.

The reviewed arts are demonstrated that the coating has only modest adherence and frequently suffers from partial or fatal barrier spallation or thermal shock cracking after relatively short periods of exposure to high temperature. This causes quality control and adherence problems. Moreover, the method of application required to produce the graded layer is tedious.

Coatings utilizing NiCrAlY and other complex aluminized coatings have been proposed (see, for example, U.S. Pat. Nos. 3,869,779 and 3,676,085). Further, U.S. Pat. No. 3,410,716 (Hiltz) discloses that zirconium dioxide can form a component of an oxide composition that bonds well to tungsten substrates. The Hiltz patent also discloses that magnesium oxide and yttrium oxide in small amounts may be utilized for stabilization purposes.

The reviewed arts are void of teaching how to prepare or select a material having a range of properties that are suitable for use in constructing a furnace for performing substantially continuous, cyclical, high temperature pyrolysis chemistry. The studied art is believed to be similarly deficient at revealing materials suitable for complex, irregular, or functionally-shaped reactor components. The art needs a materials that can endure prolonged exposure to high severity temperatures, substantial temperature swing cycles, cyclic flows of reaction materials, and concurrently provide the needed structural integrity, crystalline stability, and chemical inertness in the presence of high temperature chemical reactions that is required for large scale, high productivity applications. Lack of materials availability and selection criteria for identifying the materials for use in the reactive and most severe temperature regions of a reactor system is one of the most critical remaining issues in design and large-scale commercial operation of such reactors and processes.

In addition the pyrolysis process is difficult to control sufficiently to ensure feedstock distribution, aeration and to avoid bridging the reactor. WO 2007/081296 A1 indicates that there are generally three types of gasification process, namely updraft (in which heated air is fed upwards through the pyrolysis zone and the fuel is allowed to descend through the pyrolysis zone), downdraft (or co-flow) in which heated air and fuel enter the reaction zone from the top of the reactor and descend together through the pyrolysis zone, or fluidised bed, in which the fuel is suspended on (typically) steam, and allowed to be processed by contact with heated air. According to the prior art, there is provided a downdraft gasification process in which shredded municipal waste is allowed to descend through a pyrolysis reactor and the waste is pyrolysed in the reactor to form a condensable fraction and a combustible gas, wherein the waste is contacted in the pyrolysis reactor in a downdraft with air which has been preheated successively by heat exchange with the pyrolysis reactor and by heat exchange with exhaust gas from the pyrolysis reactor. The process according to the prior art permits the use of a reactor, which will take loose shredded feedstock with higher moisture content; this has a major impact on cost and efficiency.

A recurring problem in methods and apparatus for the pyrolysis processes is the generation of ash that tends to fuse into irregular-sized chunks, known as slag, the formation of which tends to block gas passageways and so reduce the efficiency of the pyrolysis of the solid waste materials. Another common problem which reduces pyrolysis efficiency is the buildup of condensates of tar and resin, resulting in blinding and otherwise restricting filters, grates, and gas passageways. Still another problem in the art is the production of an off gas from such solid waste pyrolysis that contains insufficient concentrations of combustible gases to comprise a useful fuel product. These and other problems are addressed and resolved by the pyrolysis reactors of the present invention, which are summarized and described in detail below.

SUMMARY OF THE INVENTION

Reactor and methods for pyrolysis of carbonaceous material are provided herein. In accordance with the present embodiment, a method for thermal processing of carbonaceous material is provided. The method comprises the steps of contacting a carbonaceous feedstock with heated inorganic heat carrier particles at reaction conditions effective for the carbonaceous feedstock to be pyrolyzed and to form a product stream comprising process gas, pyrolysis oil, and solids. The solids comprise char and cooled inorganic heat carrier particles.

The solids are separated from the product stream. An oxygen-containing gas and the solids are combined at combustion conditions effective to convert the char into ash and heat the feedstock material.

In accordance with the present embodiment, an apparatus for producing heat for rapid thermal processing of carbonaceous material is provided. The apparatus comprises a reactor that is configured to contact a carbonaceous feedstock with heated plural surfaces at reaction conditions effective for the carbonaceous feedstock to be pyrolyzed and to form a product stream comprising the process, pyrolysis oil, and solids. The solids comprise char and cooled inorganic particles. The exhaust stream comprises flue gas, entrained inorganic particles, and ash.

In the thermal coating system of the present invention the inner metal bond coating layer, which contacts the surface of the pyrolysis reactor, consists essentially of enamel frit, sand mixed with 50% solution of sodium tetra-Borat (Na₂B₄O₇), clay, titanium dioxide, and colloidal silicon dioxide (SiO₂).

The metal bond coating layer is, in turn, coated with an outer layer containing fluoroplastic F4D and oxiethylated alkylphenols (polyethylene-ethylene-alkyl phenyl ethers) (RC₆H₄O(CH₂CH₂O)_(n)H or Neonol AF 9-12 oxyethylated nonylphenol (C₉H₁₉C₆H₄O(C₂H₄O)₁₂H).

In the anti-adhesive coating system of the present invention the inner metal bond coating layer, which contacts the surface of the exhaust system, consists essentially of perfluoropolyetheric acid “6MFK-180” (CF₃O(CF₂CF₂O)_(n)CF₂COOH where n=34-35) mixed with 1,2-difluorotetracloroethane (C₂Cl₄F₂) and 1,1,2-trifluorotrichlorethane (CF₂ClCFCl₂) at the 4:1 weight ratio.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other objects and advantages and novel features of the present invention will become apparent from the following detailed description of the preferred embodiment of the invention illustrated in the accompanying drawings, wherein:

FIG. 1 is a vertical view of the pyrolysis reactor of the invention;

FIG. 2a is a vertical view taken along the FIG. 1 and with portions shown the upper level of the pyrolysis of the invention in schematic;

FIG. 2b is a vertical view taken along the FIG. 1 and with portions shown the upper level of the pyrolysis of the invention in transparent schematic;

FIG. 2c is an enlarged fragmented sectional view of the bolted flange connection;

FIG. 3a is a vertical view taken along the FIG. 1 and with portions shown the middle level of the pyrolysis of the invention in schematic;

FIG. 3b is a vertical view taken along the FIG. 1 and with portions shown the middle level of the pyrolysis of the invention in transparent schematic;

FIG. 3c is a view taken from the FIG. 1 and with portions shown the upper view of the middle level of the pyrolysis of the invention in transparent schematic;

FIG. 3d is a view taken from the FIG. 1 and with portions shown the upper view of the middle level heating elements;

FIG. 4a is a vertical view taken along the FIG. 1 and with portions shown the lower level of the pyrolysis of the invention in schematic;

FIG. 4b is a vertical view taken along the FIG. 1 and with portions shown the lower level of the pyrolysis of the invention in transparent schematic;

FIG. 4c is a view taken from the FIG. 1 and with portions shown the upper view of the lower level of the pyrolysis of the invention in transparent schematic;

FIG. 4d is a view taken from the FIG. 1 and with portions shown the side view of the lower level of the pyrolysis of the invention in transparent schematic.

DETAILED DESCRIPTION OF THE INVENTION

Specific details of several embodiments of the technology are described below with reference to FIGS. 1-4. Other details describing well-known structures and systems often associated with pyrolysis reactors have not been set forth in the following disclosure to avoid unnecessarily obscuring the description of the various embodiments of the technology. Many of the details, dimensions, angles, and other features shown in the Figures are merely illustrative of particular embodiments of the technology. Accordingly, other embodiments can have other details, dimensions, angles, and features without departing from the spirit or scope of the present technology. A person of ordinary skill in the art, therefore, will accordingly understand that the technology may have other embodiments with additional elements, or the technology may have other embodiments without several of the features shown and described below with reference to FIGS. 1-4.

For the purpose of this description the pyrolysis reactor 1 should be understood to include an upper zone (FIGS. 2a and 2b ) wherein pyrolyzable materials is heated to a temperature approximately 400° C. or 725° F., a middle zone (FIGS. 3a, 3b, 3c and 3d ) wherein dry pyrolyzable materials is heated to a temperature approximately 900° C. or 1652° F., and a lower zone (FIGS. 4a, 4b and 4c ) wherein the ash is removed. Multiple temperature sensing means (not shown) are disposed within the divided chambers (sections) of the pyrolysis reactor in order to monitor as well as control the continuous pyrolysis operation.

FIG. 1 shows a diagram of one embodiment of the apparatus of the present invention. Pyrolyzable materials, in the form of sorted municipal wastes, used tires, used plastic and plastic wastes; bituminous coal or other wood residue is initially stored dried to approximate humidity level of 18% in a feedstock preparation section (not shown). The pyrolyzable materials are grinded to the grain size of approximately 5 mm in a grinder (not shown). As shown in FIG. 1, process material is loaded into a hopper 2. The hopper 2 has a closing lid or similar arrangement for limiting free admission of air, particularly if air contamination may be a concern, and then is directed, by suitable means, such as a conveyor 3 or a vacuum system (not shown) from feedstock preparation section into an inlet of the input end of a pyrolysis reactor vessel 1, which is shown in more detail in FIG. 2a . An outlet is provided at the exit end of the reactor vessel 1 to remove ash residue. This product is the result of the thermo-chemical processes occurring within the pyrolysis reactor, which will be explained in more detail hereinafter.

The reactor vessel 1 in the embodiment shown in FIG. 1 is an elongated cylindrical tube, approximately 1600 mm or 63 inches in diameter and 7000 mm or 24 feet long. The reactor vessel comprised generally of a cylindrical steel vessel sections having a removable top head 7, each section with cooperating bolted flanges 12 that can be bolted tightly together by a plurality of studs and nuts (FIG. 2c ). The reactor vessel comprises an inert oxidation-resistant metal, such as steel 310S AISI, or titanium clad steel. In the embodiment shown, the walls of the reactor vessel 1 are 0.060 inches thick, although this dimension is not critical and can be varied substantially. Pyrolysis reactor 1 is inserted into a protective cylindrical shell and insulated by a thermal resistant material (not shown) such as ceramic fiber blankets (2600 degree Fahrenheit operating temperature) or pyrolytic graphite.

In the embodiment shown in FIG. 2a , inlet 5 is an opening having a circular or oval configuration. The diameter of the circular opening is approximately 7 inches, with the dimensions of the oval opening being commensurate. A vertical cylindrical steel protective shell 9 supported on a plurality of structural steel columns (not shown). Protective cylindrical shell 9 comprises an oxidation-resistant metal, such a steel type 304. A center shaft 6 is disposed in the centre of the upper section of the pyrolysis reactor. A removable top head 7 of the pyrolysis reactor is to prevent outside oxygen contained air mix with the granulated material undergoing first stage thermal conversion. The pyrolysis reactor 1 conventionally is equipped with a plurality of shell mounted burners 8. The burners 8 are fired utilizing either natural gas or a liquid fuel to provide the process heat required for the specific application. The burners 8 usually are equipped with gas pilots to ensure continuity of the combustion process and the burners 8 fire horizontally and quasi tangentially into the space available between the hearths 14. The gas burners 8 being employed operates either with a normal or “full burner” fuel supply or with a diminished or “fuel-starved” fuel supply during the pyrolysis cycle in a controlled manner. Exhaust gases are exiting from the burners 8 through the exhaust system 11. Exhaust valve 10 is to regulate the gas flow.

The presently preferred embodiment shown in FIG. 2b includes a conventional multiple hearth heaters 14. A plurality of hearths 14 are located within the vessel perpendicular to its axis, and spaced in the order of two (2) to five (5) feet or more depending on the application of the reactor 1. The number of hearths 14 varies and typically has ranged from a minimum of four to a maximum of seventeen. A center shaft 6 is supported by a plurality of support arms 13 parallel to the hearths 14. The double-wall air-cooled cast nodular iron or alloy center shaft 6 is mounted to rotate slowly about its vertical axis. The shaft 6 carries a number of attached rabble arms, each equipped with a set of removable alloy rabble teeth or plows. Drive means (not shown) is coupled to the upper end of the center shaft 6 to cause the center shaft to rotate so that the rabble arms urge material to travel across the hearths 14. The hearths 14 are constructed so that material flows downward through the furnace in a generally serpentine path.

Referring to FIG. 3, the present invention includes a cylindrical heater body having a recessed upper surface defining a heater chambers. The heater body 1 is fitted into a corresponding circular opening of a protective cylindrical shell. The heater chambers are substantially cylindrical chambers that are lined with insulators. The insulators are ceramic fiber blankets (2600 degree Fahrenheit operating temperature) or pyrolytic graphite. Pyrolytic graphite is an anisotropic material that conducts heat well in one direction and poorly in the transverse direction. It is installed or oriented into the heater chambers so that it conducts heat well in the direction parallel to the inner surfaces of the heater chamber and poorly in the perpendicular direction. This confines the heat within the heater chambers minimizing losses to the surrounding reactor walls, and helps ensure that the heating within the chambers are uniform.

FIG. 3a demonstrates outer arrangements of burners 8, heat conducting elements 15 and exhaust system 11, while FIGS. 3b-3d are to demonstrate internal arrangement of the heating schema. The illustrated heaters arrangement forms the overall heater unit for the middle section of the pyrolysis reactor. Such arrangement allows each heating element to be controlled separately with minimal effect on adjacent heaters. This arrangement allows each heating element (or group of elements) to be controlled separately to provide applied heat to maintain the desired axially constant reactor wall temperature. The heater control can be controlled to be responsive to the measured temperature for each reactor length segment. The improved heating method for the pyrolysis reactor can be practiced for any practical reactor size. Generally, it is expected that the operation could be low pressure due to the high operating temperatures. Utilization of the improved heating method would allow maximum reactor throughput at any size. Char/ash resulting from pyrolyzing the carbon contained in pyrolysis reactor 1 is easy to blend, easy to analyze, and easy to store. Pyrolysis reactor 1 also allows the char/ash to become a raw material rather than just a carbon enriched compounds. FIGS. 4a-4d are to demonstrate pyrolysis reactor 1 unloading schematic. During the continuous operation of the pyrolysis reactor, char/ash is being divided to four equal streams to be removed by unloading mechanism 18 (FIG. 4a ). Bottom section of the reactor 1 as shown in FIG. 4a comprised of 4 unloading shafts 17, means to remove pyrolysis gases 16 and exhaust gases removing system 11. In addition, presently preferred embodiment shown a system to introduce argon-hydrogen mix (at the volume ratio of 75:15) or air-water stem mix ((at the volume ratio of 1:1) 19. FIGS. 4b-4c is to demonstrate detailed unloading schematics. FIGS. 4c-4d is to demonstrate unloading mechanism in more details. As can be seen from FIG. 4d , the waste-feeding screws are connected to air sealed chamber 20, which is in turn, is connected to char/ash de-activation and cooling system 22. The inner surface of the pyrolysis reactor 1 according to this invention may be coated with a film in any manner provided that a uniform film of a anti adhesive substance is formed on the desired surface portions of the pyrolysis reactor, the inner wall of the retort, the hearth outer surface, middle section of the reactor, unloading mechanism and/or the air vent portion. At the present time, however, there is practically no process available whereby an anti-adhesive film of sufficiently high wear resistant properties can be formed at a speed of commercial significance over an adequately large surface area. For this reason it is recommended to use the process now to be described.

Formation of the Composite Coating for Steel

One of the tasks of the present invention is creation of the silicate basis anti adhesive protective coating with the self-sedimentation of fluoride suspension deposition on the substrate surface. The problem is solved by the introducing two layers of coating comprised of: the first layer—enamel frit (B₂O₃—40.6-42.0; CoO—0.3-0.7; Na₂O—6.0-6.5; CaO—6.0-6.5; Al₂O₃—16.0-16.8; TiO₂—23.2-24.0; Li₂O—0.3-0.7; SiO₂—5.0-6.0 of mass %), sand, clay, titanium dioxide, mix of sodium tetra-Borat (Na₂B₄O₇) and colloidal silicon dioxide (SiO₂) at the weight ratio of 1:1; the second layer—fluoroplastic F4D and oxiethylated alkylphenols (polyethylene-ethylene-alkyl phenyl ethers) (RC₆H₄O(CH₂CH₂O)_(n)H or Neonol AF 9-12 oxyethylated nonylphenol (C₉H₁₉C₆H₄O(C₂H₄O)₁₂H);

In order to prepare the first layer of the protective coating the following ratio of components (Mas. %) have been used: The first silicate layer ESP-200 enamel Frit—56.75-70.67 Sand—14.13-22.70 Clay—4.24-5.68 titanium dioxide—0.07-0.28 50% mix of sodium tetr-borate ad colloidal silicone—0.28-0.34; Second fluoroplastic layer consist of: fluoroplastic F4D brand—37.40-42.20,

The F4MD brand—9.35-12.05, oxiethylated alkylphenols 3.61-6.54, distilled water—the rest.

This silicate layer (0.15-0.30 mm thick) was applied on the grounded surface with method of a regional pouring, then was dried up and heated at a temperature of 790°±10° C., at the heating increase ratio of 50° C. per hour. Then fluoroplastic suspension was applied and dried at the temperature of 350° C. for at least 3 hours. The silicate and fluoroplastic coating has high operational properties (anti-adhesion and wear resistance). As a result, of the pyrolysis, the treated product is decomposed into a solid phase (a mixture of carbon residue that contains coke and tar, and a gaseous phase (pyrolysis gas). A part of the pyrolysis gas developed in the pyrolysis reactor is sent to the waste drier and/or to the burners 8 of the reactor for use as an additional heat carrier.

Thus it has been shown that the invention provides a novel reactor for pyrolytic processing and more efficient utilization of carbon contained wastes as compared to conventional reactors of this type. The aforementioned reactor is simple in construction, provides efficiency in the pyrolysis reaction, sufficient compaction of the waste material for displacement of air from the material being treated, efficient mixing of the material being treated, and efficient loading, unloading of the material into and from the reactor along with efficient conveyance of the material through the reactor. The structure of the reactor is characterized by a low metal-to-power ratio and hence by low manufacturing cost.

Although the invention has been shown and described with reference to specific embodiments, it is understood that these embodiments should not be construed as limiting the areas of application of the invention and that any changes and modifications are possible provided that these changes and modifications do not depart from the scope of the attached patent claims. For example, the retort and the external casing that surrounds the retort may have shapes different from those shown in the drawings and can be made from different heat-resistant materials. The loading and unloading mechanisms of the pyrolysis reactor may have structures different from those shown in FIG. 1 and FIG. 4. For example, an electric drive can be used for opening and closing the sliding gates. The sliding gates may be replaced by rotating gates pivotally installed on the inner walls of the loading hopper. The reactor sections can be assembled by inserting the male projections of one of the sections into female bores of the adjacent section.

Filing Publication Cited Patent Date Date Applicant Title U.S. Pat. No. 1,777,449 May 19, Oct. 7, W.C. Rath Process of producing 1923 1930 gas from garbage U.S. Pat. No. 3,507,929 Nov. 30, Apr. 21, J. Happel et Decoking process for a 1966 1970 all pyrolysis reactor U.S. Pat. No. 4,210,491 Oct. 16, Jul. 1, Bernard L. Method and apparatus for 1978 1980 Schulman retorting a substance containing organic matter U.S. Pat. No. 8,801,904 B2 Jul. 3, Aug. 12, Landon C.G. Chain drag system for 2012 2014 Miller, Scott treatment of carbaneous Behrens, Brian waste feedstock and method Rayles for the use thereof U.S. Pat. No. 3,156,733 A Dec. 2, Nov. 10, Happel John, Selective pyrolysis of 1960 1964 Kramer Leonard methane to acetylene and hydrogen U.S. Pat. No. 3,156,734 A May 22, Nov. 10, Happel John Pyrolysis of methane- 1961 1964 hydrogen mixtures U.S. Pat. No. 4,929,789 A Jan. 15, May 29, Victor R. Process for pyrolyzing or 1988 1990 Gupta, thermal cracking a gaseous Christopher J. or vaporized hydrocarbon Clark feedstock using a novel gas-solids contacting device and an oxidation catalyst U.S. Pat. No. 8,278,231 B2 Nov Oct 2, ChangMin Chun, Heat stable formed ceramic, 24, 2012 Frank apparatus and method of 2008 Hershkowitz using the same U.S. Pat. No. 8,450,552 B2 Oct 8, May 28, Frank Pyrolysis reactor materials 2009 2013 Hershkowitz, 4 and methods More U.S. Pat. No. 8,399,372 B2 May 18, Mar. 19, ChangMin Chun, Stabilized ceramic compo- 2009 2013 Frank sition, apparatus and Hershkowitz methods of using the same U.S. Pat. No. 8,512,663 B2 May 18, Aug. 20, ChangMin Chun, Pyrolysis reactor materials 2009 2013 Frank and methods Hershkowitz US 20090008292 A1 May 13, Jan. 8, Paul F. Pyrolysis reactor conver- 2008 2009 Keusenkothen, sion of hydrocarbon feed- 2 More stocks into higher value hydrocarbons WO 2007081296 A1 Jan. 16, Jul. 19, Omer Salman, 3 Downdraft/updraft gasifier 2006 2007 More for syngas production from solid waste U.S. Pat. No. 9,347,005 B2 Sep. 13, May 24, Sathit Methods and apparatuses for 2011 2016 Kulprathipanja, rapid thermal processing Paolo Palmas of carbonaceous material U.S. Pat. No. 4,055,705 A May 14, Oct. 25, Stephan Thermal barrier coating 1976 1977 Stecura, Curt system H. Leibert U.S. Pat. No. 3,869,779 A Jan. 24, Mar. 11, Michael A Duplex aluminized coatings 1974 1975 Gedwill, Salvatore J Grisaffe U.S. Pat. No. 3,676,085 A Feb.18, Jul. 11, Elam Richard Cobalt base coating for 1971 1972 C, Evans the super alloys Dennis U.S. Pat. No. 3,410,716 A Apr. 1, Nov. 12, Ralph H Hiltz Coating of refractory metals 1965 1968 with metal modified oxides U.S. Pat. No. 2,897,778 A Dec. 9, Aug. 4, Fritz Held, Apparatus for epilamizing 1954 1959 Willi Maag surfaces U.S. Pat. No. 3,233,584 A Jul.18, Feb 8, Ernest L. Coating process and apparatus 1958 1966 Angstadt 

1. A pyrolysis reactor for processing pyrolyzable materials in order to recover usable end products comprising: (a) a substantially cylindrical retort, extending through and stationary relative to said reactor and having an upstream end and a downstream end, each end being outside of said reactor; (b) feeding means for feeding the substance containing pyrolyzable materials into said retort, said feeding means communicating with the upstream portion of said retort; (c) means located within said retort for moving the pyrolyzable materials from the upstream portion of said retort to the downstream portion thereof; (d) solids residue removing means for removing solids residue from said retort, said solids residue removing means communicating with the downstream portion of said retort; (e) solids residue introducing means for introducing said solids residue removed from said retort, one end of said introducing means communicating with said solids residue removing means and the other end thereof communicating with the bottom portion of said retort; (f) solids residue extracting means for extracting solids residue from said retort and communicating with the lower downstream portion of said retort; (g) heating means for heating the particles; (h) usable end products means condensable hydrocarbon vapors and product gas (i) hydrocarbon vapors removing means for removing hydrocarbon vapors from said retort, said hydrocarbon vapors removing means communicating with said retort at least one point located upstream, with respect to the flow of said pyrolyzable materials in said retort, from said feeding means; (j) solids residue flow controlling means for controlling the flow of the solids residue while the solids residue is being employed as particles of the said retort such that the solids residue flow from the upstream portion to the downstream portion of said retort and in a direction substantially countercurrent to the flow within said retort of the pyrolyzable materials, said solids residue flow controlling means including at least one partition separating said retort into a plurality of successively adjacent sections, each partition which is downstream, with respect to the flow of particles in said retort; and (l) regulating means for regulating the levels of the pyrolyzable materials maintained within the said retort whereby solids residue which is in a section of said retort downstream, with respect to the flow of particles in said retort, from another section thereof may be caused to overflow into the section of the retort which is immediately downstream therefrom with respect to the flow of particles in said retort.
 2. A system according to claim 1 further including: (a) heating means to heat the granular material; and (b) heating means coupled in gas flow communication with said heating means to pyrolyze said granulated material and to produce hot gases which are transferred from said heating means; (c) classifier means coupled to receive granular material; (d) transfer means coupled to said classifier means to convey the receive granular material to said heating means.
 3. A system to heat granular material and to pyrolyze comprising: (a) multiple hearth heating means including, i. an upper zone to heat the granular material; ii. a lower zone to receive hot granular material and to pyrolyze said material; (b) classifier means coupled to receive granular material from said multiple hearth heating means; (c) transfer means coupled to said classifier means to convey the granular material to said lower zone means.
 4. A system according to claim 3 further including means to convey the hot granular material directly from said upper zone to said lower zone.
 5. A process for pyrolyze granular material comprising: (a) introducing the granular material into a heating means; (b) heating the granular material to produce hot gases; (c) transferring the hot gases from the heating means to heat the granular material; (d) transferring the hot granular material to a classifier; (e) transferring the granular material from the classifier to the heating means to be heated.
 5. The system claimed in claim 1 wherein the hydrocarbon vapors removing means communicate with said retort at a plurality of points located substantially along the said retort and downstream, with respect to the flow of said granular material in said retort, from said feeding means.
 6. The system claimed in claim 3 wherein: (a) the substance within the multiple hearth heating means of the said retort is heated to a temperature approximately 400° C. or 725° F., (b) the substance within the middle section of the said retort is heated to a temperature approximately 900° C. or 1652° F., (c) and the temperature of the section nearest the downstream end of the said retort maintained at approximately 149° C. or 300° F.
 7. The system claimed in claim 3 wherein the length of time between when the said granular material is fed into the retort and when corresponding solids residue is removed from the retort is approximately: (a) 5 to approximately 15 minutes for the said upper zone of said retort; and (b) 45 to approximately 55 minutes for the said lower zone of said retort.
 8. The system claimed in claim 3 wherein the removal of the hydrocarbon vapors is performed by removing the hydrocarbon vapors at a plurality of points located substantially along the said retort.
 9. The system claimed in claim 1, wherein the thermal coating of the said reactor the inner metal bond coating layer, which contacts the surface of the said reactor, consists essentially of enamel frit, sand mixed with 50% solution of sodium tetra-Borat (Na₂B₄O₇), clay, titanium dioxide, and colloidal silicon dioxide (SiO₂). The metal bond coating layer is, in turn, coated with an outer layer containing fluoroplastic F4D and oxiethylated alkylphenols (polyethylene-ethylene-alkyl phenyl ethers) (RC₆H₄O(CH₂CH₂O)_(n)H or Neonol AF 9-12 oxyethylated nonylphenol (C₉H₁₉C₆H₄O(C₂H₄O)₁₂H).
 10. The system claimed in claim 1, wherein the anti-adhesive coating system of the said reactor the inner metal bond coating layer, which contacts the surface of the exhaust system, consists essentially of perfluoropolyetheric acid “6MFK-180” (CF₃O(CF₂CF₂O)nCF₂COOH where n=34-35) mixed with 1,2-difluorotetracloroethane (C₂Cl₄F₂) and 1,1,2-trifluorotrichlorethane (CF₂ClCFCl₂) at the 4:1 weight ratio. 